Exploring the Mechanism of Catalysis with the Unified Reaction Valley Approach (URVA)—A Review

Autor: Elfi Kraka, Wenli Zou, Yunwen Tao, Marek Freindorf
Jazyk: angličtina
Rok vydání: 2020
Předmět:
Zdroj: Catalysts
Volume 10
Issue 6
Catalysts, Vol 10, Iss 691, p 691 (2020)
ISSN: 2073-4344
DOI: 10.3390/catal10060691
Popis: The unified reaction valley approach (URVA) differs from mainstream mechanistic studies, as it describes a chemical reaction via the reaction path and the surrounding reaction valley on the potential energy surface from the van der Waals region to the transition state and far out into the exit channel, where the products are located. The key feature of URVA is the focus on the curving of the reaction path. Moving along the reaction path, any electronic structure change of the reacting molecules is registered by a change in their normal vibrational modes and their coupling with the path, which recovers the curvature of the reaction path. This leads to a unique curvature profile for each chemical reaction with curvature minima reflecting minimal change and curvature maxima, the location of important chemical events such as bond breaking/forming, charge polarization and transfer, rehybridization, etc. A unique decomposition of the path curvature into internal coordinate components provides comprehensive insights into the origins of the chemical changes taking place. After presenting the theoretical background of URVA, we discuss its application to four diverse catalytic processes: (i) the Rh catalyzed methanol carbonylation&mdash
the Monsanto process
(ii) the Sharpless epoxidation of allylic alcohols&mdash
transition to heterogenous catalysis
(iii) Au(I) assisted [3,3]-sigmatropic rearrangement of allyl acetate
and (iv) the Bacillus subtilis chorismate mutase catalyzed Claisen rearrangement&mdash
and show how URVA leads to a new protocol for fine-tuning of existing catalysts and the design of new efficient and eco-friendly catalysts. At the end of this article the pURVA software is introduced. The overall goal of this article is to introduce to the chemical community a new protocol for fine-tuning existing catalytic reactions while aiding in the design of modern and environmentally friendly catalysts.
Databáze: OpenAIRE
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